Predicting hydrocarbon potential of an earth formation underlying a body of water by analysis of seeps containing low concentrations of methane

ABSTRACT

The present invention provides for on-site capture of methane at sea, for isotopic examination. Liquid and interfering gases are separated from the methane; the methane is oxidized to form carbon dioxide and water; and the carbon dioxide and water are isotopically analyzed for carbon and deuterium distribution to determine methane origin, as an aid to evaluation of hydrocarbon potential of an earth formation.

CROSS-REFERENCES TO RELATED APPLICATIONS

This is a continuation-in-part application of Ser. No. 135,026, filedMar. 28, 1980 for "Predicting Hydrocarbon Potential of an EarthFormation Underlying a Body of Water by Analysis of Seeps Containing LowConcentrations of Carbonaceous Gases."

SCOPE OF THE INVENTION

This invention relates to a method and apparatus--in general--forproviding for isotopic chemical analysis of methane seeping from ahydrocarbon pool or other source of organic matter associated with anearth formation underlying a body of water, and--in particular--forproviding for on-site capture of such gas whereby indications of theirbiogenic and/or thermogenic origin of the pool can be accuratelyforecasted.

In one aspect, the present invention provides for the acquisition ofhighly accurate data related to the isotopic chemistry of extremelysmall concentrations of such gas, say 1 to 10 microliters per liter ofthe sea water, being constantly collected at depth.

In another aspect, the dissolved methane can be collected in sufficientamounts utilizing vacuum separation and selective capture techniques inthe presence of an inert air carrier. The sequence of steps includes:Carbonaceous fluids are first separated from the water collected atdepth; then the methane present is quantitatively converted to gaseouscarbon dioxide and heavy water, if present. Basis of later analysis isthe isotopic composition of the ¹³ C (or ¹⁴ C) and deuterium associatedwith the collected sample. Further, since the normalized variation of ¹²C to ¹³ C (i.e., the delta ¹³ C measurement) requires less amounts ofmethane to be collected, such analytical method is preferred. The delta¹³ C measurement is defined in Petroleum Formation and Occurrence, B. P.Tissot, D. H. Welte, Springer-Verlag, N.Y., (1978) at p. 88 as: ##EQU1##

BACKGROUND OF THE INVENTION

While marine exploration systems are presently available forcontinuously sampling water seeps so as to analyze for presence ofcarbonaceous fluids such as methane, none have the capability ofproviding a compositional parameter that is uniquely diagnostic of seeporigin, and hence allowing the user/operator to distinguish thebiogenically derived sample from a sample associated with a hydrocarbonsource.

Reasons: Other interpretative tests were thought to be sufficient from acost/result standpoint. Also, the lengthy and complexed nature of thesteps involved in collecting, isolating and tagging sufficient amountsof the samples for such analysis were thought to be beyond thecapability of present on-site collection and analytical systems.

MODIFICATIONS IN ACCORDANCE WITH THE PRESENT INVENTION

When it was noted in the above-identified parent application thathydrocarbon potential of earth formations (underlying bodies of water)could be evaluated based, inter alia, on ¹³ C (or ¹⁴ C and/or delta ¹³C) content of collected methane samples, interest in shipboardcollection and analysis techniques intensified.

It has now been discovered that if the heavier isotope of hydrogen,deuterium, is also a constituent of the captured methane, then yet afurther interpretive clue to biogenic origin of the methane is provided.

Since the oxidation products of the collected methane (carried out atstation 39 of FIG. 4 of the above parent application) are gaseous carbondioxide and water, and since both such products are trapped in thesubsequent trapping station in the above-identified embodiment (i.e., atstation 40 of FIG. 4), isotopic presence of deuterium can be easilydetermined by mass spectroscopic examination around the time that thepreviously described carbon isotopic testing was performed.

SUMMARY OF THE INVENTION

In accordance with the present invention, a quick, convenient and highlyaccurate technique for the acquisition of sufficient amounts of twoconstituents of methane dissolved in sea water is provided. Result:Indications of their isotopic character--and biogenically- and/orthermogenically-derived origin of the associated pool--can be easily andsurprisingly accurately determined.

In more detail, sea water is first collected via an electro-hydrauliccable, at depth by a drone trailing from a sea-going vessel, the waterbeing pumped at a substantially constant flow rate in a range from about3 to 7 liters/minute. Up cable destination of the water: A vacuumchamber aboard the vessel where the water is broken into droplets undera slight vacuum (27-28 inches of mercury) and the gaseous constituents,liberated. These constituents are carried via an air stream to acontinuous hydrocarbon flame monitor where, if the flame monitorresponse is positive, more complexed analytical equipment is broughtinto play; e.g., a multi-port valve can be energized as to allow thedissolved gases to be analyzed chromatographically. Or still another ofthe valve ports can be activated to allow the same constituents to flowinto and through an isotropic trapping network where collection inmicroliter amounts occurs. Within the isotopic network, use is made ofthe flowing air stream (flow rate being preferably about 30 millilitersper minute in a range of 20-120 milliliters per minute). Gases ofinterest pass, in seriate, from station-to-station: Methane is isolated(by removing all interfering species), and finally converted to gaseouscarbon dioxide and heavy water, if present (in a catalytically-aidedcomplete oxidation reaction), and both are cryogenically trapped in aU-shaped trapping chamber. Next, the ends of the trapping chamber areheated and collapsed, sealing them from the atmosphere.

After being transported to a mass spectrometer, the chamber is re-openedso that isotopic analysis can occur. Using the latter results (alongwith geographic address data) allows for accurate biogenically- andthermogenically-associated predictions to be made.

DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates operation of the present invention, utilizing avessel positioned on a body of water overlying an earth formation thatcollects and analyzes, continuously, samples of water at depth;

FIG. 2 is a schematic diagram of collection and analytical operationsattendent on-site collection of water samples by the vessel of FIG. 1;and

FIGS. 3-5 are detailed drawings of an isotopic capture network of theassociated on-site collection and analytical operations of FIG. 2.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

FIG. 1 illustrates the present invention.

As shown, a drone 10 is positioned at a depth Z₀ below a vessel 11floating at the surface 12 of the body of water 13. Within the drone 10,is a pump (not shown). The purpose of the pump: To draw water samplesinterior of the drone 10 and pump them upcable (via electrohydrauliccable 14) to a diagnostic system 15 aboard the vessel 11.

In addition to pumping equipment, the drone 10 is fitted with variousoceanagraphic devices, including a depth sensor; a current monitor isalso provided that includes a bottom-oriented sonar device incombination with an electromagnetic sensor for measuring the speed anddirection of the ocean currents relative to the bottom. Signals fromthese devices pass via conductors in the side walls of the cable 14 soas to provide annotation (both visual and on tape), associated withgeographic position (of the drone and/or the vessel), depth of thedrone, etc., as shown. In that way, accurate geographic addresses forthe samples as a function of drone and/or vessel location, is assured.

Diagnostic system 15 also provides for a series of geochemical tests,and includes vaccum separation system 16 and a gas phase analysisnetwork 17. Key to diagnostic results using network 17: determinationthat hydrocarbon gases are present and what types (using hydrocarbonanalyzer system 18) in combination with a gas chromatagraph 19, and thenisotopic examination via isotopic capture network 20.

FIG. 2 illustrates operation of diagnostic system 15 in still moredetail.

As shown, vacuum separation system 16 includes an air-tight chamber 21for separating the water into liquid and gas phases. Entry and egressfrom the chamber 21 via a series of inlets and outlets 21A-21C. Inlet21A receives the water samples via cable 14 and associated manifold 22.A nozzle 24 breaks water into droplets. Note that even though the flowrate of the water can be as high as 7 liters per minute, usual flow rateis usually about 3.7 liters per minute. The separated liquid phase isdischarged from the chamber 21 via outlet 21B and pump 25. The gas phaseexits via outlet 21C through vacuum pump 26 and exhaust manifold 27 inthe presence of a wet air carrier.

Also of importance in the operation of diagnostic system 15: storage anddisplay of all annotation data via the electrical network/display 34 toallow for determination of geographic addresses of all samples taken bythe drone, as previously explained.

Manifold 27 includes an arm 28 which terminates in a continuouslyoperating hydrogen flame ionization analyzer 18. Remaining arm 29 of themanifold 27 terminates at multi-port valve 30.

One port 31 of the valve 30 is open to the atmosphere. Another port 32is disconnectably connected to gas chromatagraph 19 which, whenoperating, providing gas chromatograms. Yet another port 33 of the valve30 is disconnectably connected to isotopic capture system 20 of thepresent invention.

Since the gas chromatograph 19 as used in association with operations ofthe present invention is usual, that is, the gas chromatograph 19provides chromatograms of hydrocarbon components in the water, emphasisof description is placed on isotopic analysis system 20 of the presentinvention.

FIG. 3 illustrates how easily isotopic capture system 20 can betransported aboard a vessel 11 in either an assembled or unassembledstate and be effectively operated in any type of environment. And sinceall functions associated with the isotopic capture system 20 occuraboard a sea-going vessel often in a hostile environment, constructionalaspects related to portability, reliability and ruggedness are of someimportance.

As shown, the capture system 20 includes a series of trapping andstripping stations 35-40 mounted to upright front panel 50 of carry-oncapture box 51. The box 51 includes side, top and back panels 52, whichform an enclosure interior thereof, wherein equipment associated withoperations can be stowed either temporarily as during transport (orpermanently as required). Carry handle 53 facilitates hand-transport ofthe box 51 to and from the vessel. Note also that the front panel 50intersects bottom panel 58 near its center. Hence, not only can theoperator use bottom panel 58 as a floor for equipment associated withstations 35-40, but also he can place a separate cover 54 (shown inphantom line) in attachment with the panels 52, 58 as when transport ofthe box is required. In that way, the equipment comprising the stations35-40 can be protected against breakage during transport. Note that thecover 54 has extending side and top panels 55 of reverse orientationwith respect to the shape provided the side, top and bottom panels.Result: Disconnectably connecting hinges 56 can be aligned with mounts57 to releasably attach the cover 54 with respect to the panels 50, 52and 58.

FIG. 4 illustrates operation of stages 35-40 of system 20 in moredetail.

Assume the operator has allowed dissolved gases to enter the sytem 20via valve 60 to station 35 to begin operations.

The key to isotopic operation of system 20 lies in quantitativeoxidation of the dissolved "signature" gas of interest, i.e., methane,as within oxidation station 39 and subsequent collection at station 40,of selected oxidants thereof. These operations occur after sinusoidaltravel of all the collected, dissolved gases via the intermediatestations 35-38 as set forth below. The usual flow rate of the gas samplewithin system 20 is about 30 microliters per minute. The amount ofcollection at station 40 is dependent on the methane concentration inthe sample sea water, the flow rate of the air carrier system, and theseparation efficiency of the vacuum separation system aboard the vessel.If the normal methane concentration is 1 microliter per liter of water,and the extraction rate of the drone is 7 liters per minute at depth,then 10 minutes will be needed to collect about 50 microliters of thegas of interest at station 40, assuming extraction efficiency at thevacuum system of 75%. In the vicinity of modest gas seeps, theconcentration of methane can easily approach 10 microliters per liter ofwater (STP) particularly in deep water. A background sample typicallycontaining 0.2 microliters of methane will take 50 minutes to collect.

Briefly with reference to FIG. 4, the wet air carrier and the dissolvedgases from the vacuum separation center enters station 35 at inlet 61.At the station 35, the gases perculate downwardly through the series ofabsorbent materials 62 supported in upright tube 63. Materials 62 removeboth water vapor and molecular carbon dioxide. Next, the carbon monoxidewhich also occurs in variable abundance in water, is removed at station36 by oxidation to carbon dioxide; the latter is subsequently removedfrom the carrier system after passing via valve 64 to station 37. Thecarrier gas stream containing both air gases and low molecular weightalkanes is then directed to stage 38 after passage through valve 65.

At the station 38, the lower, mid- and higher-range molecular weighthydrocarbons are removed, that is, all hydrocarbons above C₁. Theremaining methane then enters station 39 where it is oxidized to gaseouscarbon dioxide and water. After passage through valve 66 the latter issubsequently retained at station 40. The details of operation of stages35-40 will now be presented in more detail below.

STATION 35

Purpose: To trap water vapor and molecular carbon dioxide in the gasphase of the separated sample. The station 35 is constructed of the tube62 attached to the front panel 50 of capture box 51 upright position,see FIG. 3, the tube 63 usually being constructed of standard wall pyrextubing. A bed of absorbent materials 62 is held in place by small wadsof glass wool 67 placed at the ends of the tube 63. The absorbentmaterials 62 are conventional and are available in the industry forremoving water vapor (viz calcium chloride, CaCl₂) and for absorbingmolecular carbon dioxide (namely, sodium hydroxide, NA(OH)). Mixtureratio 1:1.

STATION 36

Purpose: To remove carbon monoxide which occurs in variable amounts insea water using a flow-through furnace system 70.

As shown in detail FIG. 5, furnace 70 consists of a helix 71 wound abouta quartz tube 72, the tube being previously wrapped with a single layerof asbestos tape 73. The helix 71 is then covered with additionalasbestos tape 74 as well as with a glass wool matting 75 forming asidewall into which a thermocouple (not shown) can be inserted. The endsof the helix 71 and the thermocouple are electrically connected tothermal controller 76 of FIG. 4. The controller 76 supplies regulatedpower to the furnace as a function of temperature. At the remainingannular space between the sidewalls of the wool matting 75 and the glasstube of the system 70 are positioned cupric oxide wire 77 along withplatinized alumina pellets 78. The pellets 78 are placed at thedownstream end of the tube 70, and held by quartz wool, not shown. Thefurnace operates about 125° C. whereby the carbon monoxide is oxidizedto carbon dioxide.

STATION 37

Purpose: To remove carbon dioxide previously generated at station 36.Station 37 is constructed of a glass tube 80 filled with an absorbentmaterial 81 such as sodium hydroxide, Na(OH), held in place with glasswads 82, and is similar in construction to station 35 previouslydescribed.

STATION 38

Purpose: To remove lower-, mid- and high-range molecular weighthydrocarbons. Station 38 is constructed of a metallic tube 83 filledwith inert chromatographic glass beads 84 in a size range of 60-80 meshheld in place by glass wool wads (not shown). When removal of low- mid-and high-range hydrocarbons is desired (removal of all hydrocarbonsabove C₁) a bath 85 consisting of liquid argon (-180° C.) orisopentane-liquid nitrogen slush (-160° C.) is placed circumferentiallyabout the bed of beads 84.

If desired, station 38 can be by-passed via valve 65. Hence, clean-up ofthe tube 83 can be facilitated, i.e., a clean gas can be passed viavalve 65 through the tube 83 while the bed of beads 84 is heated to atemperature of about 200°-300° C. for several minutes. Note that attemperatures above 400° C. however, the beads 84 will soften.

STATION 39

Purpose: To completely oxidize the methane of interest to gaseous carbondioxide and water. The station 39 includes a furnace 86. It is similarin design and construction to the furnace 70 of station 36 shown indetail in FIG. 5, except that furnace 86 operates at temperatures inexcess of 600° C. in a catalytically aided reaction. The temperaturepreferred is about 650° C. Result: Methane is quantitatively convertedto carbon dioxide at a lower operating temperature than would be normal,due in part to the effect of the cupric oxide helix and platinizedalumina beads used as catalysts within the furnace 86. In this regard,it should be noted the combustion efficiency of the furnace 86 atdifferent ranges and temperatures has been tested. A standardhydrocarbon mixture consisting of say 66 parts per million methane, 10parts per million C₂ H₆, 10 parts per million C₃ H₆, and 10 parts permillion C₄ H₁₀ in a helium carrier, was passed through furnace 86 at 30milliliters per minute. The test was repeated at 20 milliliters perminute. The vent of the furnace 86 was connected to a gas chromatographequipped with a flame ionization detector. At the maximum sensitivity ofthe detector (approximately 0.5 parts per million CH₄ equivalent) withthe above mixture flowing through the furnace 86 at the above rates, nomethane was detected at the detector. The condition continued as long ascombustion furnace 86 was above 600° C., say preferably 650° C. Largeramounts of methane were syringe-injected (say up to 400 microliters ofmethane) into the furnace with similar results. Thus, it is concludedthat furnace 86 will quantitatively oxidize all methane concentrationsthat are likely to be obtained in the field.

STATION 40

Purpose: To trap microliter quantities of carbon dioxide and heavywater, if any, oxidized at station 39.

Station 40 is constructed of a glass tube 87 bent into a U-shape. Itsarms connect to transfer tubes 88 (and its inlet and outlet,respectively) which facilitate gas passage through the tube 87. The tube87 is also filled with inert chromatographic grade glass beads 89 ofaverage size, say 60-80 mesh forming a trapping bed. Beads 89 are heldin place by wads of glass wool (not shown). Collection of the gaseouscarbon dioxide and water is effected by immersing the tube 87 and beads89 in a bath 90 of either liquid argon at -180° C. or anisopentane-liquid nitrogen slush at -160° C. Note that at the outlet ofthe station 40, the transfer tube 88 connects via valve 91 to either (i)flow meter 92 and vent 93 or (ii) to a vacuum pump (not shown). Duringcollection, item (i), above, is connected to the tube 87. After thecollection is complete, the valve 91 is operated to connect the interiorof the tube 87 to the vacuum pump and the latter is turned on. Thetransfer tubes 88 are then sealed by heating them with a smalloxy-propane torch. At a mass spectrometer site, the contents of the tube87 (carbon dioxide and water vapor) and impurities, if they exist, (airgases, primarily) are introduced into a vacuum line where the carbondioxide can be purified prior to isotopic analysis, if desired. Prior toreusing the tube 87 and beads 89, both are heated to 200°-300° C. in thestream of clean air to remove organic contaminents. Note that cryogenictrapping by bath 90 can present some problems if the bath temperaturesare not maintained within a range of -160° to -180° C. For example, ithas been found that at higher temperatures (say -125° C.) using anisopentane-liquid nitrogen slush, the carbon dioxide can break throughthe tube 87 to vent 93 at modest flow rates, say 16 milliliters perminute. At lower temperatures, say -196° C., oxygen can condense on thebeads 89 interrupting the carrier flow. Carbon dioxide has been foundquantitatively to be retained on the beads 89 at -160° C. using anisopentane-liquid nitrogen slush, for 25 minutes at flow rates of about100 milliliters per minute.

Thus, at air carrier flow rates of 20-30 milliliters per minute, thecarbon dioxide will be retained for periods of two hours or more.Moreover, at -180° C., the retention time of carbon dioxide willundoubtedly increase if liquid argon (-180° C.) is used.

EXPERIMENTAL DATA

An investigation of isotopic fractionation associated with system 20 ofFIG. 4, has been undertaken, such investigation utilizing standard 5%methane-argon and 10% methane-argon mixtures. Results of isotopicexamination are as set forth below in Table I.

                  TABLE I                                                         ______________________________________                                                                    Recovery                                                                              δ.sup.13 C(PDB)                     Sample #                                                                              Std        Vol. Inj.                                                                              %       ‰                                ______________________________________                                        HC-11   5% CH.sub.4 /Ar                                                                           50      100     -39.31                                    HC-12   5% CH.sub.4 /Ar                                                                           50      100     -39.27                                    HC-13   5% CH.sub.4 /Ar                                                                          100      100     -36.36                                    HC-14   5% CH.sub.4 /Ar                                                                          100      100     -39.57                                    HC-23   10% CH.sub.4 /N.sub.2                                                                    100      100     -26.07                                    HC-24   10% CH.sub.4 /N.sub.2                                                                    100      100     -25.45                                    HC-25   10% CH.sub.4 /N.sub.2                                                                    100      100     -25.53                                    HC-26   10% CH.sub.4 /N.sub.2                                                                    100      100     -26.73                                    Ref-1   10% CH.sub.4 /N.sub.2                                                                    --       100     -30.50                                    Ref-2   10% CH.sub.4 /N.sub.2                                                                    --       100     -28.11                                    Ref-3   10% CH.sub.4 /N.sub.2                                                                    --       100     -29.13                                    ______________________________________                                    

Samples HC-11 through HC-14 show good agreement and demonstrate a highlevel of precision at two concentration levels of 50 microliters and 100microliters of the carbon dioxide (STP). Mean and standard deviations ofthe delta ¹³ C composition were -39.38±0.13. Reference samples have notyet been analyzed.

Samples HC-23 through HC-26 and reference samples 1-3, provide similarresults except the delta ¹³ C distributions were systematically"lighter" by a value of -3.57°/°°. There is, at present, no explanationfor the systematic bias noted above.

In a parallel study, sea water saturated with a methane/argon mixture attwo temperatures (18° C. and 2° C.) was stripped of its dissolvedmethane. The dissolved methane was then condensed to carbon dioxide atan air carrier flow rate of 30 milliliters per minute. Approximately 30%of the methane was removed from solution in 10 minutes. Results ofisotopic examination are set forth below with reference to Table II.

                  TABLE II                                                        ______________________________________                                                                    Recovery                                                                              δ.sup.13 C(PDB)                     Sample #                                                                              Std        Vol. Inj.                                                                              %       ‰                                ______________________________________                                        HC-15   5% CH.sub.4 /Ar                                                                          1495.sup.a                                                                             32      -40.16                                    HC-19   5% CH.sub.4 /Ar                                                                          2180.sup.a                                                                             30      -39.17                                    ______________________________________                                         .sup.a = saturation concentrations in 1 liter sea water at 18° and     2° C.                                                             

Note that samples HC-15 and HC-19 represent partially stripped sea waterpreviously equillibrated with the 5% methane/argon mixture, the samemixture used to obtain the results in Table I. But also note that theresults of Table II are not significantly different than those obtainedfor samples HC-11 through HC-14 of Table I which were achieved using thesame source tank of methane/argon. Of particular interest in Tables Iand II, is the fact that the fractionation associated with incompletestripping of the samples HC-15 and HC-19 in Table II is less than 1°/°°.This is expected since the fractionation factor is about 1.03 (or thesquare root of 17/16). That is to say, for small methane strippingefficiences (less than 1%), the resulting carbon dioxide will be 3°/°°lighter than the parent methane. At 30% recoveries, the fractionation iswithin experimental error.

Isotopic fractionation is dependent on vapor pressures of C₁₂ H₄ and C₁₃H₄, each of which being temperature dependent. At temperature extremeslikely to be encountered at the surface of the earth (-2° C. to 45° C.),isotopic fractionation associated with gas extraction should be withinexperimental error. It is also worth noting that success of the presentinvention does not depend on the absolute delta C¹³ values provided foreither the biogenic or thermogenic methane fractions. Relative changesin a local region are the focus of interest.

From the above, it is apparent from the invention as herein beforedescribed that variations are readily apparent to those skilled in theart, and hence the invention is not limited to combinations hereinbefore described but should be given the broadest possibleinterpretation in terms of the following claims.

We claim:
 1. Method of on-site collection and examination of small concentrations of methane dissolved in water so as to predict hydrocarbon potential of an earth formation underlying a body of water, said formation being a source of said methane, comprising:(i) at a known geographic location continuously sampling said water at a selected flow rate and at a selected depth; (ii) continuously vacuum separating said water into liquid and gas phases; (iii) quantitatively separating interfering gas species from said methane at a series of separating stations by conveying said separated gas phase of step (ii) via an air carrier vented to atmosphere and flowing at a known flow rate, in seriation to and through said separating stations; (iv) quantitatively oxidizing said methane at an oxidizing station; (v) cryogenically trapping gaseous oxidants of step (iv) in the form of carbon dioxide and water vapor at a trapping station; and (vi) isotopically analyzing said trapped oxidants of step (v) for carbon and deuterium distribution so as to determine biogenic and/or thermogenic origin of said methane and thereby aid in the evaluation of the hydrocarbon potential of said earth formation.
 2. Method of claim 1 in which said air carrier of step (iii) is also used to convey the separated methane of step (iii) to the oxidizing station of step (iv) and the resulting oxidants of step (iv) to the trapping station of step (v).
 3. The method of claim 2 in which the flow rate of said air carrier is from 20-120 microliters per minute and a cryogenic capture period for trapping said oxidants is sufficiently long to trap at least 10 microliters of said carbon dioxide.
 4. Method of claim 1 in which said cryogenic trapping temperature of step (v) is from about -160° C. to about -180° C. at air carrier flow rates from about 20-120 microliters per minute.
 5. Method of claim 1 in which step (iii) related to separation of gas species that might interfere with accurate trapping of said methane, includes the sub-steps of:(i') removing water vapor and molecular carbon dioxide from passing gas in the presence of said air carrier; (ii') oxidizing carbon monoxide to carbon dioxide; (iii') trapping the carbon dioxide of step (ii'); and (iv') cryogenically trapping out all low-, mid-, and high-range molecular weight hydrocarbons above C₁.
 6. Method of claim 1 in which the oxidation of said methane in step (iv) is catalytically assisted.
 7. Method of claim 1 in which cryogenic trapping of oxidants of methane in step (v) includes the sub-steps of:(a) interrupting venting of said air carrier to the atmosphere, by connecting a downstream end to a vacuum pump; (b) with said vacuum pump operating, sealing both upstream and downstream ends of the cryogenic trapped carbon dioxide and water vapor; and (c) removing said trapped carbon dioxide and water vapor to a mass spectrometer for isotopic examination.
 8. Method of claim 7 in which said isotopic examination provides delta ¹³ C value and deuterium distribution of said oxidized methane.
 9. Method of on-site collection and examination of small concentrations of methane dissolved in sea water so as to predict hydrocarbon potential of an earth formation, said formation containing a hydrocarbon pool that is the source of said methane, comprising:(i) at known geographic locations continuously sampling said sea water at depth; (ii) continuously vacuum separating said collected sea water into liquid and gas phases; (iii) continuously monitoring said gas phase of said separated water for the presence of hydrocarbons; (iv) if hydrocarbons are present, quantitatively separating out all interfering gas species to the detection of methane and its oxidation products, carbon dioxide and water vapor; (v) quantitatively oxidizing said methane to carbon dioxide and water and then cryogenically trapping the resulting carbon dioxide and water vapor in the presence of an air mixture flowing at a rate of about 20 to 120 milliliters per minute; and (vi) isotopically examining the carbon and deuterium distribution of said oxidized methane, so as to determine its biogenic and/or thermogenic origin.
 10. Method of claim 9 in which said isotopic examination of step (vi) provides a series of delta ¹³ C and deuterium values indexed to known geographic locations associated with said sampling locations of step (i).
 11. Method of claim 9 in which step (iv) includes the following sub-steps performed in sequence in the presence of an air carrier having a flow rate between about 20 and 120 milliliters per minute:(a) removing water vapor and molecular carbon dioxide from said gas phase of said separated water, by passing same through a bed of absorbent materials; (b) oxidizing any carbon monoxide to carbon dioxide by passing said gas phase through a catalytically-aided oxidation oven, maintained at mid-temperatures; (c) removing the carbon dioxide of step (b) by passing the gas phase through another bed of absorbent material; and (d) cryogenically trapping out all low-, mid-, and high-range molecular weight hydrocarbons above C₁, by passing the gas phase through an inert bed of beads maintained at extremely low temperatures, whereby all interfering gas species in said gas phase are removed prior to oxidation of said methane.
 12. Method of claim 11 in which step (v) includes the sub-steps of:(a) oxidizing said methane to carbon dioxide and water vapor by passing said methane and air mixture through a catalytically-aided oxidation oven maintained at a selected temperature range; and (b) cryogenically trapping out said carbon dioxide and water vapor of sub-step (a) by passing them through an inert bed of glass beads maintained at extremely low temperatures.
 13. Method of claim 12 in which said cryogenic-trapping temperatures of sub-step (b) is in a range between about -160° C. and -180° C. 